废催化剂常含有一定量的积碳和硫,因此在回收处理时多采用焙烧处理脱碳脱硫.在焙烧含W,Mo,Ni,Co的废催化剂过程中会产生一定量的复合氧化物,此外新型钼酸镍、钼酸钴、钨酸镍催化剂也在大量使用.这类钨、钼酸盐由于稳定性较高,采用已有工艺极难处理.针对此类复合氧化物的分解问题,绘制了25℃下Me-Mo(W)-H2O系和Me-Mo(W)-NH3-H2O系Me-Mo(W)-EDTA-H2O系的热力学平衡图,并对NiMoO4,CoMoO4,NiWO4的碱浸出和配合物浸出进行了热力学分析.研究结果表明:NaOH分解的难易顺序为NiWO4＞ CoMoO4＞ Ni-MoO4;氨可极大地降低NiMoO4,CoMoO4,NiWO4在水溶液中的稳定性,氨性溶液中Ni,Mo,Co,W的平衡浓度比水溶液中提高了1×102～1×104倍(pH约为8～11),其分解难易次序为NiWO4＞ NiMoO4＞ CoMoO4;EDTA同样可极大提高NiMoO4,CoMoO4,NiWO4在水溶液分解的Ni,Co,Mo平衡浓度,在EDTA总浓度为1 mol·L-1的条件下,NiMoO4,CoMoO4分解的最高Ni,Co平衡浓度为1 mol·L-1,而NiWO4最高Ni平衡浓度仅为l×10-Y08 mol·L-1([Y]T =1 mol·L-1),3种复合氧化物在EDTA水溶液中分解的难易顺序为NiWO4＞ NiMoO4＞ CoMoO4.碱分解、氨浸出以及EDTA配合物浸出均可选择性浸出NiMoO4,CoMoO4,而NiWO4则需要采用同时回收载体氧化铝的高压高碱分解法.
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